CN110030743B - Preparation method and application of MOFs (metal-organic frameworks)/biomass-based carbon composite photothermal conversion material based on interface photothermal conversion - Google Patents
Preparation method and application of MOFs (metal-organic frameworks)/biomass-based carbon composite photothermal conversion material based on interface photothermal conversion Download PDFInfo
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- CN110030743B CN110030743B CN201910310845.3A CN201910310845A CN110030743B CN 110030743 B CN110030743 B CN 110030743B CN 201910310845 A CN201910310845 A CN 201910310845A CN 110030743 B CN110030743 B CN 110030743B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/14—Treatment of water, waste water, or sewage by heating by distillation or evaporation using solar energy
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S70/00—Details of absorbing elements
- F24S70/10—Details of absorbing elements characterised by the absorbing material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
- Y02A20/208—Off-grid powered water treatment
- Y02A20/212—Solar-powered wastewater sewage treatment, e.g. spray evaporation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/40—Solar thermal energy, e.g. solar towers
Abstract
The invention discloses a preparation method and application of an MOFs/biomass-based carbon composite photothermal conversion material based on interface photothermal conversion. The invention takes biomass as raw material, and prepares biomass-based carbon material through pretreatment and high temperature; dispersing biomass-based carbon powder in MOFs precursor solution to prepare the MOFs/biomass-based carbon composite photothermal conversion material; uniformly dispersing the mixture on the upper surface of polymer foam wrapping filter paper or non-woven fabric to obtain a light absorber capable of floating on the water surface, and then carrying out interface photo-thermal conversion to obtain solar distilled water. The method utilizes hydrophilic modification of MOFs to biomass-based carbon to prepare the photothermal conversion material, the composite photothermal conversion material is the photothermal conversion material, a heat-insulating material is used for insulating water and heat, and filter paper or non-woven fabric is used for conveying water, so that solar distilled water can be simply, rapidly and repeatedly obtained, the method is expected to become an effective measure for solving the shortage of fresh water resources, and meanwhile, an idea can be provided for high-value-added application of biomass.
Description
Technical Field
The invention relates to the field of photo-thermal conversion, in particular to a preparation method and application of an MOFs/biomass-based carbon composite photo-thermal conversion material based on interface photo-thermal conversion.
Background
Solar energy is taken as the most abundant renewable clean resource on the earth, and the most applied in recent years are photoelectric conversion and photothermal conversion. Due to the shortage of fresh water resources, there is a trend to obtain fresh water by evaporating water through solar photo-thermal conversion. The traditional solar water evaporation technology generally utilizes sunlight to directly heat water, the photo-thermal conversion efficiency is not high, and the fresh water obtaining amount is very little. With the development of material technology, plasma nano materials, carbon-based materials, biomimetic materials and the like with photo-thermal conversion performance are used in solar water evaporation. These materials generally take two forms: (1) dispersing in water for local photo-thermal conversion; (2) floating on water surface for interface light-heat conversion. Local light-heat conversion because the material disperses in the water, and light conversion's heat directly passes to the water around, causes calorific loss, still needs to heat whole water in addition. The interface photo-thermal conversion can effectively avoid the direct transfer of the heat of the photo-conversion to the water body, and the photo-thermal conversion efficiency is obviously improved, so that the development trend of obtaining fresh water resources by evaporating water in the mode becomes.
In order to be practical, the photothermal conversion efficiency and cost effectiveness of the material must be considered. Biomass-based carbon materials are receiving much attention because of their advantages such as low cost, high light absorption, and stable structure. However, most still have the problem of poor hydrophilicity.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of an MOFs/biomass-based carbon composite photothermal conversion material based on interface photothermal conversion, which is used for compounding MOFs with good hydrophilicity and stable structure with biomass-based carbon to improve the hydrophilicity of a carbon material. The MOFs/biomass-based carbon composite photothermal conversion material is placed on the upper surface of a support body made of a heat insulating material wrapping filter paper or non-woven fabric and used as a solar absorber. The xenon lamp is used for simulating sunlight, the sunlight directly irradiates the solar absorber floating on the surface of water to perform interface photo-thermal conversion, the filter paper or the non-woven fabric is used for transmitting water, the heat loss is reduced by the heat insulating material, the photo-thermal conversion efficiency is further improved, and the water evaporation rate is increased.
The invention is realized by the following technical scheme:
a preparation method of MOFs/biomass-based carbon composite photothermal conversion material based on interface photothermal conversion comprises the following steps:
(1) biomass is taken as a raw material, impurities are removed, washing and drying are carried out, pretreatment is carried out, or high-temperature treatment carbonization is directly carried out in gas, so as to prepare a biomass-based carbon material;
(2) and dispersing the biomass-based carbon material in the MOFs precursor solution to prepare the MOFs/biomass-based carbon composite photothermal conversion material.
Preferably, in step (1), the biomass comprises waste crop vegetable sponge, soybean straw or bamboo.
Preferably, in step (1), the pretreatment is a soaking treatment by HCl solution or KOH solution of different concentrations.
Preferably, in the step (1), the high-temperature treatment carbonization is carried out at the temperature of 400-1000 ℃ for 1-3 h, and the gas can be nitrogen, argon or carbon dioxide.
Preferably, the precursor solution in step (2) is MOF801, ZIF8, MOF303 or MOF841 which is stable in hydrophilic structure.
The specific steps of the step (1) are as follows: peeling raw materials of towel gourd, removing seeds, washing with distilled water, drying, cutting into 3-4cm length, placing in a porcelain boat, placing in a tube furnace, and placing in a N-shaped furnace2At 5 deg.C for min under atmosphere-1Heating to 800 ℃, keeping the temperature for 2h, then cooling to room temperature, drying to obtain the loofah sponge-based carbon material, and grinding into powder.
The specific steps of the step (2) are as follows: mixing the components in a molar ratio of 1:1 ZrOCl2 .8H2Adding O and fumaric acid into a formic acid and N, N-dimethylformamide solution to prepare a precursor solution, dispersing 0.2-1 mg of the luffa based carbon powder material into 20-100 ml of MOF801 precursor solution, magnetically stirring in constant-temperature water baths at different temperatures for 6-10 h, washing, and drying in vacuum to obtain the MOF 801/luffa based carbon composite photothermal conversion material.
The invention also discloses the composite photothermal conversion material prepared by the preparation method.
The composite photothermal conversion material is applied to the solar absorber, the heat insulation material is used as the heat insulation and water isolation material, the heat insulation material is wrapped by the filter paper or the non-woven fabric, and the MOFs/vegetable sponge based carbon composite photothermal conversion material is uniformly dispersed on the upper surface layer to prepare the light absorber floating on the water surface.
Preferably, a filter paper or a non-woven fabric is wrapped around a polymer circular foam having a diameter of 4cm and a thickness of 2cm, and 20mg of MOFs/biomass-based carbon powder is dispersed on the upper surface layer. Preparing a light absorber, placing in a 50ml beaker filled with tap water, placing on an electronic balance connected with a computer and capable of recording data in real time, vertically irradiating on the solar absorber with simulated sunlight for 1h at an ambient temperature of 25 deg.C, a humidity of 40%, a tap water temperature of 25 deg.C and a water evaporation rate of 3.8253 kg · m-2·h-1. The sunlight is simulated by a xenon lamp, and the light intensity is 1kW/m2 ~10 kW/m2。
Advantageous effects
1. According to the invention, biomass such as vegetable sponge, corn straw and bamboo rod is used as a precursor to prepare the biomass-based carbon material, and the biomass-based carbon material is compounded with MOFs with good hydrophilicity and stable structure to improve the hydrophilicity.
2. The invention takes MOFs/biomass-based carbon material as a photo-thermal conversion material, a heat insulation material as heat insulation and water isolation, filter paper or non-woven fabric wraps the outside of the heat insulation material to transmit water, and the photo-thermal conversion material is uniformly dispersed on the upper surface to prepare the light absorber. The design enables the light absorber to float on the water surface, utilizes interface photo-thermal conversion, can fully utilize the converted heat energy, improves the solar energy utilization rate, accelerates the evaporation rate, and has the water evaporation rate of 3.8253 kg.m-2·h-1。
Drawings
FIG. 1 is a side view of a light absorber;
FIG. 2 is an SEM image of the vegetable sponge-based carbon material of example 1;
FIG. 3 is an SEM image of the MOFs/vegetable sponge-based carbon composite photothermal conversion material;
FIG. 4 is a graph of water evaporation versus time for the materials of example 1 and comparative example 1;
FIG. 5 is a graph of temperature of the upper layer of the light absorber over time for example 1;
fig. 6 is an SEM image of the bamboo pole-based carbon material prepared in example 2;
FIG. 7 is an SEM image of a composite material prepared in example 2;
fig. 8 is a graph showing the change in the amount of water evaporated with time in example 2, comparative example 2 and comparative example 3.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
(1) Removing outer skin and seeds from vegetable sponge, soaking in distilled water, washing to remove impurities, drying, cutting into pieces with consistent length and size(3-4 cm), placing in a porcelain boat, placing in a tube furnace, and introducing N2Raising the temperature to 800 ℃ at the heating rate of 5 ℃/min, preserving the temperature for 2h, and then cooling to room temperature to obtain the loofah-based carbon material (the SEM image of the material is shown in figure 2). 2mmol of ZrOCl2.8H2O and 2mmol fumaric acid (molar ratio is 1: 1), dispersing 0.2-1 mg of a loofah sponge-based carbon powder material in a solution of 10ml formic acid and 20ml N, N-dimethylformamide in a solution of 20-100 ml of a precursor of MOF801, magnetically stirring for 6-10 h in constant-temperature water baths at different temperatures, washing with methanol, and vacuum drying at 60 ℃ for 24h to obtain the MOF 801/loofah sponge-based carbon composite photothermal conversion material.
(3) Wrapping filter paper with cylindrical polystyrene foam with the diameter of 4cm and the thickness of 2cm, uniformly dispersing 20mg of MOF 801/loofah-based carbon composite photothermal conversion material on the upper surface layer to prepare a light absorber, placing the light absorber in a 50ml beaker filled with tap water, placing the beaker on an electronic balance which is connected with a computer and can record data in real time, simulating sunlight by using a xenon lamp, wherein the thickness of the beaker is 1kW/m2Is irradiated on the light absorber perpendicularly for 1 h. The ambient temperature was 25 ℃, the humidity was 40%, and the tap water temperature was 25 ℃.
Comparative example 1
Wrapping filter paper with cylindrical polystyrene foam with diameter of 4cm and thickness of 2cm, uniformly dispersing 20mg of loofah-based carbon composite photothermal conversion material on the upper surface layer to obtain a light absorber, placing the light absorber in a 50ml beaker filled with tap water, placing the beaker on an electronic balance connected with a computer and capable of recording data in real time, and simulating sunlight by using a xenon lamp at 1kW/m2Is irradiated on the light absorber perpendicularly for 1 h. The ambient temperature was 25 ℃, the humidity was 40%, and the tap water temperature was 25 ℃.
Performance test 1
As can be seen from FIG. 4, the data of the change of the water evaporation amount with time in comparative example 1 and comparative example 1 were analyzed, respectively, and the strength was 1kW/m2When the carbon material and the MOF 801/vegetable sponge-based carbon material are irradiated for 1 hour under a xenon lamp light source, the water evaporation capacity of the carbon material and the MOF 801/vegetable sponge-based carbon material is respectively 0.9807g and 1.7951g, namely the water evaporation rate is 0.7891kg m-2·h-1And 1.4289 kg·m-2·h-1. Experimental data show that the evaporation capacity of pure water in unit area and time is small, the evaporation capacity of the carbon material can be obviously improved, but the evaporation capacity of the MOF801 modified loofah sponge-based carbon composite photothermal conversion material is improved more.
Example 2
(1) Cutting the obtained bamboo into 2cm pieces, cleaning with distilled water, and drying at 80 deg.C for 24 hr. Soaking in 6mol/L KOH solution for 24h, drying at 80 deg.C, placing in a ceramic boat, placing in a tube furnace, introducing N2Raising the temperature to 800 ℃ at a heating rate of 5 ℃/min, preserving the temperature for 2h, and then cooling to room temperature to obtain the bamboo-rod-based carbon material (SEM of the material is shown in figure 6). Adding 2mmol of zinc acetate and 2mmol of 2-methylimidazole into 50ml of N, N-dimethylformamide solution to prepare liquid precursor solution, dispersing 0.2g of bamboo-based carbon powder material into 50ml of ZIF8 precursor solution, adding the mixed solution into a 100 ml hydrothermal reaction kettle, keeping the temperature of 160 ℃ in a drying oven for 8 hours, washing with methanol for 3 times, and drying in vacuum at 60 ℃ to obtain the ZIF 8/bamboo-based carbon composite photothermal conversion material (SEM of the material is shown in figure 7).
(3) Wrapping filter paper with cylindrical polystyrene foam with diameter of 4cm and thickness of 2cm, uniformly dispersing 20mg MOFs/bamboo rod-based carbon composite photothermal conversion material on the upper surface layer to obtain a light absorber, placing the light absorber in a 50ml beaker filled with tap water, placing the beaker on an electronic balance connected with a computer and capable of recording data in real time, simulating sunlight with a xenon lamp, and allowing the temperature of the beaker to be 1kW/m2Is irradiated on the light absorber perpendicularly for 1 h. The ambient temperature was 25 ℃, the humidity was 40%, and the tap water temperature was 25 ℃.
Comparative example 2
Wrapping cylindrical polystyrene foam with diameter of 4cm and thickness of 2cm with filter paper, dispersing 20mg ZIF8 in the upper surface layer to obtain light absorber, placing in 50ml beaker filled with tap water, placing the beaker on an electronic balance connected with computer and capable of recording data in real time, simulating sunlight with xenon lamp at 1kW/m2Is irradiated on the light absorber perpendicularly for 1 h. The ambient temperature was 25 ℃, the humidity was 40%, and the tap water temperature was 25 ℃.
Comparative example 3
Wrapping filter paper with cylindrical polystyrene foam with diameter of 4cm and thickness of 2cm, uniformly dispersing 20mg of bamboo rod-based carbon composite photothermal conversion material on the upper surface layer to obtain a light absorber, placing the light absorber in a 50ml beaker filled with tap water, placing the beaker on an electronic balance connected with a computer and capable of recording data in real time, simulating sunlight by using a xenon lamp, wherein the thickness of the beaker is 1kW/m2Is irradiated on the light absorber perpendicularly for 1 h. The ambient temperature was 25 ℃, the humidity was 40%, and the tap water temperature was 25 ℃.
Performance test 2
As can be seen from FIG. 8, by analyzing the data of the change of the water evaporation amount with time in comparative example 2, comparative example 2 and comparative example 3, respectively, the strength was 1kW/m2When irradiated for 1 hour under a xenon lamp light source, the water evaporation amounts of the ZIF8, the bamboo-based carbon material and the ZIF 8/bamboo-based carbon material are 0.7745g, 1.7016g and 1.8434g respectively, that is, the water evaporation rate is 0.6163 kg m-2·h-1、1.3543 kg·m-2·h-1And 1.4671 kg m-2·h-1. Experimental data show that the evaporation amount of pure ZIF8 and bamboo-based carbon materials is small in unit area and time, while the evaporation amount of water of the ZIF8 modified bamboo-based carbon composite photothermal conversion material is improved most.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (4)
1. A preparation method of a MOF 801/loofah-based carbon composite photothermal conversion material based on interface photothermal conversion is characterized by comprising the following steps:
(1) peeling raw materials of towel gourd, removing seeds, washing with distilled water, drying, cutting into 3-4cm length, placing in a porcelain boat, placing in a tube furnace, and placing in a N-shaped furnace2At 5 deg.C for min under atmosphere-1Rate of temperature rise ofHeating to 800 ℃, keeping the temperature for 2h, cooling to room temperature, drying to obtain the vegetable sponge-based carbon material, and grinding into powder to prepare the biomass-based carbon material;
(2) mixing the components in a molar ratio of 1:1 ZrOCl2 .8H2Adding O and fumaric acid into a formic acid and N, N-dimethylformamide solution to prepare a precursor solution, dispersing 0.2-1 mg of the luffa based carbon powder material into 20-100 ml of MOF801 precursor solution, magnetically stirring in constant-temperature water baths at different temperatures for 6-10 h, washing, and drying in vacuum to obtain the MOF 801/luffa based carbon composite photothermal conversion material.
2. The MOF 801/loofah-based carbon composite photothermal conversion material prepared by the preparation method of claim 1.
3. An application of the MOF 801/loofah-based carbon composite photothermal conversion material in a solar absorber according to claim 2, wherein a heat insulating material is used as a heat insulating and water isolating material, the heat insulating material is wrapped by filter paper or non-woven fabric, and the MOF 801/loofah-based carbon composite photothermal conversion material is uniformly dispersed on an upper surface layer to form a light absorber capable of floating on a water surface.
4. The use according to claim 3, wherein the filter paper or the non-woven fabric is wrapped with polystyrene or polyurethane polymer cylindrical foam having a diameter of3 to 10cm and a thickness of 0.5 to 3cm, 6 to 100 mg of the MOF 801/loofah-based carbon composite photothermal conversion material powder is uniformly dispersed on the upper surface of the polymer foam wrapped with the filter paper or the non-woven fabric to prepare the light absorber, and the light absorber is placed in a container filled with water.
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| CN113353912A (en) * | 2021-06-18 | 2021-09-07 | 北京化工大学 | Preparation method and application of porous carbon material with high light-heat conversion efficiency |
| CN113943024A (en) * | 2021-10-28 | 2022-01-18 | 中国科学技术大学 | Application of bamboo joint wall in efficient photothermal conversion water evaporation device and water evaporation device |
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